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Publication numberUS5240544 A
Publication typeGrant
Application numberUS 07/870,120
Publication dateAug 31, 1993
Filing dateApr 17, 1992
Priority dateApr 5, 1988
Fee statusLapsed
Publication number07870120, 870120, US 5240544 A, US 5240544A, US-A-5240544, US5240544 A, US5240544A
InventorsYoshio Tanimoto, Nobuyuki Yoshida, Mitsuji Tsuji, Eiichi Usuda, Kouji Satou
Original AssigneeSumitomo Chemical Company, Limited
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Adhesive composition
US 5240544 A
Abstract
An adhesive composition comprising a modified, ethylene/α-olefin copolymer rubber or a modified, ethylene/α-olefin/non-conjugated diene copolymer rubber containing 0.1-10% by weight of at least one member selected from the group consisting of an acid anhydride and a dicarboxylic acid, and, if necessary, as an amine compound,
(i) 0.2-2 moles of a dialkylamine per mole of the acid anhydride in said modified copolymer rubber when said modified copolymer rubber contains no dicarboxylic acid;
(ii) 0.2-2 moles of a polyamine compound per mole of the total amount of the acid anhydride and the dicarboxylic acid in said modified copolymer rubber; or
(iii) 0.2-2 moles of a dialkylamine per mole of the acid anhydride in said modified copolymer rubber and 0.2-2 moles of a polyamine compound per mole of the acid anhydride in said modified copolymer rubber when said modified copolymer rubber contains no dicarboxylic acid. The above adhesive composition exhibits good adhesion for rubber compositions, particularly low unsaturated, non-polar rubber compositions and fibers, and is excellent in storage stability.
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Claims(26)
What is claimed is:
1. A method of adhering an ethylene/α-olefin copolymer rubber or an ethylene/α-olefin-diene terpolymer rubber to one member selected form the group consisting of an ethylene/α-olefin copolymer rubber, and ethylene/α-olefin/diene terpolymer rubber, nylon fibers, polyester fibers, nylon plain cloth and polyester plan cloth,
which method comprises using, as an adhesive, a composition comprising a modified, ethylene/α-olefin copolymer rubber or a modified, ethylene/α-olefin/non-conjugated diene copolymer rubber, either rubber containing 0.1-10% by weight of an olefinically unsaturated acid anhydride and 0.81-1 moles of a dialkylamine per mole of the acid anhydride, and an organic solvent wherein said dialkylamine is selected from the group consisting of diethylamine and dibutylamine.
2. A method according to claim 1, wherein the α-olefin has 3-10 carbon atoms.
3. A method according to claim 1, wherein the α-olefin is propylene.
4. A method according to any one of claims 1, 2 and 3, wherein the non-conjugated diene is selected from the group consisting of dicyclopentadiene, ethylidenenorbornene and 1,4-hexadiene.
5. A method according to claim 4, wherein the olefinically unsaturated acid anhydride is selected from the group consisting of maleic anhydride, citraconic anhydride and nadic anhydride.
6. A method according to claim 4, wherein the olefinically unsaturated acid anhydride is maleic anhydride.
7. A method according to claim 4, wherein the dialkylamine is diethylamine.
8. A method according to claim 4, wherein the dialkylamine is dibutylamine.
9. A method according to claim 4, wherein the organic solvent is selected from the group consisting of toluene, xylene, hexane, cyclohexane, pentane, benzene, ethylbenzene, ethyltoluene, cumene, diethylbenzene, chloroform and tetrachloromethane.
10. A method according to any one of claims 1, 2 and 3, wherein the non-conjugated diene is ethylidenenorbornene.
11. A method according to claim 10, wherein the olefinically unsaturated acid anhydride is selected from the group consisting of maleic anhydride, citraconic anhydride and nadic anhydride.
12. A method according to claim 10, wherein the olefinically unsaturated acid anhydride is maleic anhydride.
13. A method according to claim 10, wherein the dialkylamine is dibutylamine.
14. A method according to claim 10, wherein the dialkylamine is diethylamine.
15. A method according to claim 10, wherein the organic solvent is selected from the group consisting of toluene, xylene, hexane, cyclohexane, pentane, benzene, ethylbenzene, ethyltoluene, cumene, diethylbenzene, chloroform and tetrachloromethane.
16. A method according to any one of claims 1, 2 and 3, wherein the olefinically unsaturated acid anhydride is selected from the group consisting of maleic anhydride, citraconic anhydride and nadic anhydride.
17. A method according to claim 16, wherein the dialkylamine is diethylamine.
18. A method according to claim 16, wherein the dialkylamine is dibutylamine.
19. A method according to claim 16, wherein the organic solvent is selected from the group consisting of toluene, xylene, hexane, cyclohexane, pentane, benzene, ethylbenzene, ethyltoluene, cumene, diethylbenzene, chloroform and tetrachloromethane.
20. A method according to any one of claims 1, 2 and 3, wherein the olefinically unsaturated acid anhydride is maleic anhydride.
21. A method according to claim 20, wherein the dialkylamine is dibutylamine.
22. A method according to claim 20, wherein the dialkylamine is diethylamine.
23. A method according to claim 20, wherein the organic solvent is selected from the group consisting of toluene, xylene, hexane, cyclohexane, pentane, benzene, ethylbenzene, ethyltoluene, cumene, diethylbenzene, chloroform and tetrachloromethane.
24. A method according to any one of claim 1, 2 and 3, wherein the dialkylamine is dibutylamine.
25. A method according to claim 24, wherein the organic solvent is selected from the group consisting of toluene, xylene, hexane, cyclohexane, pentane, benzene, ethylbenzene, ethyltoluene, cumene, diethylbenzene, chloroform and tetrachloromethane.
26. A method according to any one of claims 1, 2 and 3, wherein the organic solvent is selected from the group consisting of toluene, xylene, hexane, cyclohexane, pentane, benzene, ethylbenzene, ethyltoluene, cumene, diethylbenzene, chloroform and tetrachloromethane.
Description

This application is a continuation of application Ser. No. 07/501,958, filed Mar. 29, 1990 now abandoned, which in turn is a division of prior application Ser. No. 07/331,599, filed Mar. 31, 1989 now abandoned.

The present invention relates to an adhesive composition suitable for adhering rubber compositions and fibers. More particularly, the present invention relates to an adhesive composition suitable for adhering rubber compositions each consisting of a low unsaturated, non-polar rubber such as an ethylene/α-olefin copolymer rubber, an isobutylene/isoprene copolymer rubber or the like.

As an adhesive for rubber compositions, etc., there has been widely used an adhesive composition consisting mainly of a polymer material containing a halogenated compound. However, the above adhesive composition does not exhibit sufficient adhesion for all the rubber compositions. Particularly, it does not exhibit sufficient adhesion for rubber compositions each consisting of the above-mentioned low unsaturated, non-polar rubber.

The present inventors have investigated an adhesive composition suitable for adhering rubber compositions, particularly rubber compositions each consisting of a low unsaturated, non-polar rubber.

An object of the present invention is to provide a novel adhesive composition consisting mainly of an ethylene/α-olefin copolymer or ethylene/α-olefin/non-conjugated diene copolymer rubber containing an acid anhydride and/or a dicarboxylic acid and which exhibits good adhesion for rubber compositions each consisting of a low unsaturated, non-polar rubber and fibers.

Other objects and advantages of the invention will become apparent from the following description.

According to the present invention, there is provided an adhesive composition comprising a modified, ethylene/α-olefin copolymer or modified, ethylene/α-olefin/non-conjugated diene copolymer rubber containing 0.1-10% by weight of an acid anhydride and/or a dicarboxylic acid (hereinafter referred to as the modified copolymer rubber).

The present invention further provides an adhesive composition comprising said adhesive composition and an organic solvent.

In the present specification, the ethylene/α-olefin copolymer rubber and the ethylene/α-olefin/non-conjugated diene copolymer rubber are hereinafter referred to as the copolymer rubbers, collectively.

The α-olefins may preferably be those having 3-10 carbon atoms. Specifically, the α-olefin includes propylene, 1-butene, 1-pentene, 1-hexene and the like.

The non-conjugated diene includes dicyclopentadiene, ethylidenenorbornene, 1,4-hexadiene, and the like.

The acid anhydride includes maleic anhydride, citraconic anhydride, nadic anhydride and the like.

The dicarboxylic acid includes maleic acid, fumaric acid, itaconic acid, citraconic acid, nadic acid and the like.

The amount of the acid anhydride and/or the dicarboxylic acid in the modified copolymer rubber is in a range of 0.1-10% by weight. When the amount is smaller than 0.1% by weight, the adhesive strength is lower and when the amount is larger than 10% by weight, a great enhancement of the adhesive strength is not expected. The amount is preferably in a range of 0.2-8% by weight, more preferably, in a range of 0.5-5% by weight.

The modified copolymer rubber in the present invention may be produced by a conventional reaction. For example, the modified copolymer rubber can be produced according to the methods described in Japanese Patent Application Kokoku No. 58-53005 and Japanese Patent Application Kokoku No. 58-445, etc.

The modified copolymer rubber containing a dicarboxylic acid alone can be easily produced by hydrolyzing the modified copolymer rubber containing an acid anhydride, too.

Also, the modified copolymer rubber containing both the acid anhydride and the dicarboxylic acid can be produced by controlling the degree of hydrolysis.

Further, a modified copolymer rubber comprising an alkenyl aromatic monomer such as styrene, methylstyrene or the like and an acid anhydride and/or a dicarboxylic acid can be preferably used, which are produced according to the method described in Japanese Patent Application Kokai No. 62-112614.

In order to improve storage stability to maintain high adhesive strength, the modified copolymer rubber containing an acid anhydride and no dicarboxylic acid may contain a dialkylamine.

The dialkylamine used in the present invention includes dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, di-t-butylamine, di-sec-butylamine, diamylamine, dihexylamine, dioctylamine and the like. Diethylamine, dipropylamine and dibutylamine are preferable.

The amount of the dialkylamine used is in a range of 0.2-2 moles, preferably 0.5-1.5 moles and more preferably 0.8-1.2 moles per mole of the acid anhydride in the modified copolymer rubber which contains no dicarboxylic acid. When the amount is smaller than 0.2 mole, the enhancement of the storage stability is smaller and when the amount is larger than 2 moles, the adhesive strength is lower.

The reaction of the dialkylamine with the modified copolymer rubber which contains no dicarboxylic acid can be conducted merely by adding the dialkylamine to a solution of the modified copolymer rubber which contains no dicarboxylic acid in an organic solvent, for example, an aromatic hydrocarbon solvent such as toluene, xylene, ethylbenzene or the like; or an aliphatic hydrocarbon solvent such as hexane, heptane, octane, decane or the like. Preferably, the above reaction is conducted with heating and stirring.

In the present invention, a polyamine compound may be added to the modified copolymer rubber in order to improve adhesion ability.

The polyamine compound used in the present invention includes aliphatic polyamine compounds and aromatic polyamine compounds. Specifically, the aliphatic polyamine compounds include ethylenediamine, triethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, trimethylhexamethylenediamine, diethylenetriamine, dipropylenetriamine, triethylenetriamine, tetraethylenepentamine, dimethylaminopropylamine, diethylaminopropylamine, hexamethylenediamine carbamate, ethylenediamine carbamate, N,N'-dicinnamylidene-1,6-hexanediamine and the like; and the aromatic polyamine compounds include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine and the like. Hexamethylenediamine and hexamethylenediamine carbamate are preferred.

The amount of the polyamine compound added is in a range of 0.2-2 moles per mole of the total amount of the acid anhydride and the dicarboxylic acid in the modified copolymer rubber. Preferably, the amount is in a range of 0.25-1.5 moles, more preferably in a range of 0.3-1 mole. When the amount is smaller than 0.2 mole, the enhancement of the adhesive strength is smaller and when the amount is larger than 2 moles, the adhesive strength cannot be expected to be enhanced proportionally to the amount.

In the present invention, the organic solvents may generally be aliphatic solvents, aromatic solvents, halogen-containing solvents and the like. Specifically, the organic solvent includes pentane, hexane, cyclohexane, benzene, toluene, xylene, ethylbenzene, ethyltoluene, cumene, diethylbenzene, chloroform, tetrachloromethane and the like. The concentration of the adhesive composition in the solution is in a range of 5-50% by weight and is selected depending upon the molecular weight of the modified copolymer rubber contained in the adhesive composition and a process for coating the adhesive composition.

The adhesive composition of the present invention may optionally comprise reinforcing agents, fillers, softening agents, tackifiers and the like which are known in the adhesive industry and the rubber industry.

The adhesive composition of the present invention exhibits good adhesion for rubber compositions, particularly rubber compositions each containing a low unsaturated, non-polar rubber such as ethylene/α-olefin copolymer rubbers, ethylene/propylene/diene terpolymer rubbers (EPDM), isobutylene/isoprene rubber or the like. Specifically, for these rubbers, the adhesive composition is excellent in vulcanization adhesion between an unvulcanized rubber composition and a vulcanized one, adhesion of two vulcanized rubber compositions to each other, vulcanization adhesion between an unvulcanized rubber composition and a natural fiber or a synthetic fiber, adhesion between a vulcanized rubber composition and a natural fiber or a synthetic fiber, and the like.

Also, the adhesive composition of the present invention can be applied to the adhesion of two natural fibers to each other, two synthetic fibers to each other and between a natural fiber and a synthetic fiber.

The present invention is explained more specifically below referring to Examples and Comparative Examples.

EXAMPLES 1-7 and COMPARATIVE EXAMPLES 1-4

The compositions of adhesives used in the Examples and Comparative Examples are shown in Table 1.

To a maleic anhydride-containing ethylene/propylene or a ethylene/propylene/non-conjugated diene copolymer rubber was optionally added an additive with a roll and then the required amount of an organic solvent as shown in Table 1 was added to attain the solids concentration as shown in Table 1. The resulting mixture was heated at 50° C. for 8 hours to form a solution. The solutions obtained are hereinafter referred to as adhesive compositions A-C.

Adhesive composition D was obtained by allowing the maleic anhydride-containing modified copolymer rubber to stand at a temperature of 60° C. and a humidity of 80% for 1 hour in a thermo-hygrostat and thereafter dissolving the modified copolymer rubber in the organic solvent under the above conditions.

Adhesive composition E for comparison was obtained by dissolving an ethylene/α-olefin copolymer rubber in toluene in the same manner as above.

The compositions of rubber adherends are shown in Table 2. Compounding agents A were mixed in a BR-type Banbury mixer, and thereto were added compounding agents B using a 8-in roll. The obtained unvulcanized rubber composition was subjected to press vulcanization under the vulcanizing conditions shown in Table 2 to obtain a vulcanized sheet having a size of 150 mm×150 mm×2 mm. From the sheet, a sample strip having a size of 20 mm×150 mm was made using a die cutter.

As a textile adherend, a sample strip having a size of 40 mm×200 mm was cut from a textile.

One of the adhesive compositions A-E shown in Table 1 was coated uniformly on the sample strip of vulcanized rubber adherend using a glass bar. In adhesion of two vulcanized rubbers to each other, two sample strips were coated with an adhesive composition and, 30 minutes thereafter, the coated surfaces of the two sample strips were placed one on the other.

In adhesion of a vulcanized rubber adherend to a textile adherend, two sample strips were coated with an adhesive composition, and immediately thereafter, the coated surfaces were placed one on the other.

And then, every contacted sample strips were intimately pressed by having a handroller of 2 kg in weight pass over and return three times thereon and the strips were then cured under the conditions shown in Table 3.

In adhesion of a vulcanized rubber adherend to a textile adherend, after curing, the excess portion of the textile adherend was trimmed with scissors to leave it the same size as that of the sample strip of the vulcanized rubber adherend.

The adhesive strength of the adhered product was measured by a 180° peeling test at a peeling speed of 50 mm/min according to JIS K 6301.

The results obtained are shown together in Table 3.

EXAMPLES 8-12 and COMPARATIVE EXAMPLES 5-7

Sheets of 2 mm in thickness were made using a 8-in roll from the unvulcanized EPDM compositions A and B shown in Table 2. These sheets were cut in a size of 150×150 mm.

In adhesion of an unvulcanized rubber composition adherend to a vulcanized rubber composition adherend, the adhesive composition of Table 1 was applied using a glass bar at a surface of each sheet of the unvulcanized rubber composition adherend and the vulcanized rubber composition adherend each having a size of 150×150 mm. After the sheets were allowed to stand for 30 minutes, they were contacted with each other. The sheets were intimately pressed by having a handroller of 2 kg in weight pass over and return three times thereon. Thereafter the unvulcanized rubber composition adherend was vulcanized at 160° C. for 30 minutes in pressurized air of 3 kgf/cm2.

In adhesion of an unvulcanized rubber composition adherend to a textile adherend, the adhesive composition was applied to the sheet of the unvulcanized rubber composition adherend. Immediately, the textile adherend having a size of 150×150 mm was placed thereon, pressed and vulcanized in the same manner as above. From the resulting sheet, a sample strip having 20×150 mm was made using a die cutter. The adhesive strength of the adhered product was measured by a 180° peeling test at a peeling speed of 50 mm/min according to JIS K 6301. The results obtained are shown together in Table 4.

EXAMPLES 13-15 and COMPARATIVE EXAMPLES 8-9

A textile sample as shown in Table 5 was cut in a size of 150×150 mm. One of the adhesive compositions A, C and E of Table 1 was applied uniformly to the textile sample using a glass bar, and immediately thereafter, the textile sample was placed on another textile sample to which no adhesion composition had been applied. And the resulting assembly was cured under the conditions shown in Table 5. From the assembly a sample strip having a size of 20×150 mm was made using a die cutter.

The adhesive strength was measured by a 180° peeling test at a peeling speed of 50 mm/min. The results obtained are shown together in Table 5.

EXAMPLES 16-21 and COMPARATIVE EXAMPLES 10-13

The compositions of adhesives used in the Examples and the Comparative Examples are shown in Table 6.

To a maleic anhydride-containing ethylene/propylene or ethylene/propylene/non-conjugated diene copolymer rubber reacted with a dialkylamine was optionally added an additive with a roll and then the required amount of an organic solvent as shown in Table 6 was added to attain the solids concentration as shown in Table 6. The resulting mixture was heated at 50° C. for 8 hours to form a solution. The solutions obtained are hereinafter referred to as adhesive compositions F-H.

Adhesive composition E for comparison was obtained by dissolving an ethylene/α-olefin copolymer rubber in toluene in the same manner as above.

The compositions of rubber adherends are shown in Table 2. Compounding agents A were mixed in a BR-type Banbury mixer, and thereto were added compounding agents B using a 8-in roll. The obtained unvulcanized rubber composition was subjected to press vulcanization under the vulcanizing conditions shown in Table 2 to obtain a vulcanized sheet having a size of 150 mm×150 mm×2 mm. From the sheet, a sample strip having a size of 20 mm×150 mm was made using a die cutter.

As a textile adherend, a sample strip having a size of 40 mm×200 mm was cut from a textile.

One of the adhesive compositions E-H shown in Table 6 was coated uniformly on the sample strip of vulcanized rubber adherend using a glass bar. In adhesion of two vulcanized rubbers to each other, two sample strips were coated with an adhesive composition and, 30 minutes thereafter, the coated surfaces of the two sample strips were placed one on the other.

In adhesion of a vulcanized rubber adherend to a textile adherend, two sample strips were coated with an adhesive composition, and immediately thereafter, the coated surfaces were placed one on the other.

And then, every contacted sample strips were intimately pressed by having a handroller of 2 kg in weight pass over and return three times thereon and the strips were then cured under the conditions shown in Table 7.

In adhesion of a vulcanized rubber adherend to a textile adherend, after curing, the excess portion of the textile adherend was trimmed with scissors to leave it the same size as that of the sample strip of the vulcanized rubber adherend.

The adhesive strength of the adhered product was measured by a 180° peeling test at a peeling speed of 50 mm/min according to JIS K 6301.

The results obtained are shown together in Table 7.

EXAMPLES 22-25 and COMPARATIVE EXAMPLES 14-16

Sheets of 2 mm in thickness were made using a 8-in roll from the unvulcanized EPDM compositions A and B shown in Table 2. These sheets were cut in a size of 150×150 mm.

In adhesion of an unvulcanized rubber composition adherend to a vulcanized rubber composition adherend, the adhesive composition of Table 6 was applied using a glass bar at a surface of each sheet of the unvulcanized rubber composition adherend and the vulcanized rubber composition adherend each having a size of 150×150 mm. After the sheets were allowed to stand for 30 minutes, they were contacted with each other. The sheets were intimately pressed by having a handroller of 2 kg in weight pass over and return three times thereon. Thereafter the unvulcanized rubber composition adherend was vulcanized at 160° C. for 30 minutes in pressurized air of 3 kgf/cm2.

In adhesion of an unvulcanized rubber composition adherend to a textile adherend, the adhesive composition was applied to the sheet of the unvulcanized rubber composition adherend. Immediately, the textile adherend having a size of 150×150 mm was placed thereon, pressed and vulcanized in the same manner as above. From the resulting sheet, a sample strip having 20×150 mm was made using a die cutter. The adhesive strength of the adhered product was measured by a 180° peeling test at a peeling speed of 50 mm/min according to JIS K 6301. The results obtained are shown together in Table 8.

EXAMPLES 26-28 and COMPARATIVE EXAMPLES 17-18

A textile sample as shown in Table 9 was cut in a size of 150×150 mm. One of the adhesive compositions A, C and E of Table 1 was applied uniformly to the textile sample using a glass bar, and immediately thereafter, the textile sample was placed on another textile sample to which no adhesion composition had been applied. And the resulting assembly was cured under the conditions shown in Table 9. From the assembly a sample strip having a size of 20×150 mm was made using a die cutter.

The adhesive strength was measured by a 180° peeling test at a peeling speed of 50 mm/min. The results obtained are shown together in Table 9.

EXAMPLES 29-32

An experiment was carried out to investigate the storage stability of an adhesive composition before and after the reaction with a dialkylamine. The compositions of the adhesive compositions used and the results obtained are shown in Table 10.

200 g of an adhesive composition was charged into a 500-ml Erlenmeyer flask with a ground stopper and allowed to stand at room temperature for 30 days. The storage stability was estimated based on whether or not precipitates and turbidity were caused and on the change of a solution viscosity as measured at 25° C.

It is clarified that the modified copolymer rubber containing an acid anhydride reacted with a dialkylamine has high adhesion strength and improved storage stability.

EXAMPLES 33-40 and COMPARATIVE EXAMPLES 19

The compositions of the modified copolymer rubber-containing compositions used are shown in Table 11.

An additive was optionally added to a maleic anhydride-containing modified copolymer rubber, and then a required amount of an organic solvent was added thereto so as to attain the solids concentration shown in Table 11. The resulting mixture was heated at 50° C. for 8 hours to form a solution, to obtain adhesive composition K, M or N. Also, adhesive composition L was obtained by allowing the maleic anhydride-containing modified copolymer rubber containing the additive to stand at a temperature of 60° C. and at a humidity of 80% for 1 hour in a thermo-hygrostat and then dissolving the modified copolymer rubber in the organic solvent under the above conditions.

Adhesive composition O for comparison was prepared by dissolving an α-olefin copolymer in toluene under the above conditions.

The compositions of rubber adherends used are shown in Table 2. Compounding agents A as shown in Table 2 were mixed in a BR-type Banbury mixer, and thereto, compounding agents B as shown in Table 2 were added to the resulting mixture using a 8-in roll. The obtained unvulcanized rubber composition was subjected to press vulcanization under the vulcanizing conditions shown in Table 2 to obtain a vulcanized sheet having a size of 150 mm×150 mm×2 mm. From the sheet, a sample strip having a size of 20 mm×150 mm was made using a die cutter.

As a textile adherend, a sample strip having a size of 40×200 mm was cut from a textile.

In accordance with one of the compositions of the adhesive compositions shown in Table 12, a diamine compound which is the polyamine compound was added to one of the adhesive compositions of Table 11, and the resulting mixture was stirred to obtain a uniform mixture. The mixture was coated uniformly on the above sample strip of a vulcanized rubber adherend using a glass bar. In adhesion of two vulcanized rubber adherends to each other, two sample strips were coated with an adhesive composition and allowed to stand for 30 minutes, after which the coated surfaces of the sample strips were placed one on the other.

In adhesion of a vulcanized rubber adherend to a textile adherend, the adhesive composition was applied to the sheet of the vulcanized rubber composition sample strip. Immediately, the textile sample strip having a size of 150×150 mm was placed thereon. The contacted sample strips were intimately pressed by having a handroller of 2 kg in weight pass over and return three times thereon and the strips were then cured under the conditions shown in Table 12.

In adhesion of a vulcanized rubber adherend to a textile adherend, after curing, the excess portion of the textile adherend was trimmed with scissors to leave it the same size as that of the sample strip of the vulcanized rubber adherend.

The adhesive strength of the adhered product was measured by a 180° peeling test at a peeling speed of 50 mm/min according to JIS K 6301.

The results obtained are shown together in Table 12.

EXAMPLES 41-44

Sheets of 2 mm in thickness were made using a 8-in roll from the unvulcanized EPDM compositions A and B shown in Table 2. These sheets were cut in a size of 150×150 mm.

In adhesion of an unvulcanized rubber composition adherend to a vulcanized rubber composition adherend, the adhesive composition of Table 13 was applied using a glass bar at a surface of each sheet of the unvulcanized rubber composition adherend and the vulcanized rubber composition adherend each having a size of 150×150 mm. After the sheets were allowed to stand for 30 minutes, they were contacted with each other. The sheets were intimately pressed by having a handroller of 2 kg in weight pass over and return three times thereon. Thereafter the unvulcanized rubber composition adherend was vulcanized at 160° C. for 30 minutes in pressurized air of 3 kgf/cm2.

In adhesion of an unvulcanized rubber composition adherend to a textile adherend, the adhesive composition was applied to the sheet of the unvulcanized rubber composition adherend. Immediately, the textile adherend having a size of 150×150 mm was placed thereon, pressed and vulcanized in the same manner as above.

From the resulting sheet, a sample strip having 20×150 mm was made using a die cutter. The adhesive strength was measured by a 180° peeling test at a peeling speed of 50 mm/min according to JIS K 6301. The results obtained are shown together in Table 13.

EXAMPLES 45-48 and COMPARATIVE EXAMPLE 20

A textile was cut in a size of 150×150 mm. The textile was coated uniformly with the final adhesive composition of Table 14 with a glass bar, and immediately thereafter placed on a textile having a size of 150×150 mm which had not been coated with the adhesive composition. The resulting assembly was cured under the conditions shown in Table 14. A sample strip having a size of 20×150 mm was made therefrom with a die cutter. The adhesive strength was measured by a 180° peeling test at a peeling speed of 50 mm/min. The results obtained are shown in Table 14.

It is clarified by these examples that the adding of a polyamine compound increases the adhesion strength.

                                  TABLE 1__________________________________________________________________________The modified copolymer rubber               Acid anhydride and/or       Amount of               dicarboxylic acid and                           Non-conjugated                                      Additive and                                                  SolidsAdhesive Intrinsic       propylene               the amount thereof                           diene and  amount Organic                                                  concentrationcomposition viscosity*1       (% by weight)               (% by weight)                           iodine number                                      (phr)  solvent                                                  (% by__________________________________________________________________________                                                  weight)A     1.4   22      Maleic anhydride                           None       None   Toluene                                                  13               1.3B     1.4   22      Maleic anhydride                           None       FEF black 20                                             Toluene                                                  10               1.0C     1.1   40      Maleic anhydride                           None       None   Toluene                                                  11               4.7D     1.6   27      Maleic anhydride                           Ethylideneorbornene                                      None   Xylene                                                   8               0.9               Maleic acid  5               0.3E     1.4   22      None        None       None   Toluene                                                  13__________________________________________________________________________ Note: *1 The intrinsic viscosity was measured at 30° C. in toluene.

                                  TABLE 2__________________________________________________________________________Compounding EPDM composition                 EPDM composition                           IIR compositionagents      A (phr)   B (phr)   (phr)__________________________________________________________________________EPDM I*1       100       --        --EPDM II*2       --        100       --IIR*3  --        --        100FEF black   150       120       90Nipsil VN3*4       --        30        --Paraffin-type process oil       100       100       30zinc oxide  5         5         5Stearic acid       1         1         1diethylene glycol       --        1         --BZnBDC*5       2         2         --TMTD*6 0.5       0.5       1.5DPTT*7 0.5       0.5       --MBT*8  1         1         1Sulfur      1.5       1.5       1.3Vulcanization       170° C. × 10 min                 170° C. × 10 min                           160° C. × 10 minconditions__________________________________________________________________________ Note: *1 EPDM I: ethylene/propylene/ethylidenenorbornene terpolymer [ethylene/propylene ratio: 70/30; the ethylidenenorbornene content: 5% by weight; Mooney viscosity (ML1+4 121° C.): *2 EPDM II: ethylene/propylene/ethylidenenorbornene [ethylene/propylene ratio: 64/45; the ethylidenenorbornene content: 10% b weight; Mooney viscosity (ML1+4 100° C.): *3 IIR: isobutylene/isoprene rubber [unsaturation degree: 1.5%; Mooney viscosity (ML1+4 127° C.): *4 Hydrous silica made by Nippon Silica. *5 Zinc din-butyldithiocarbamate *6 Tetramethylthiuram disulfide *7 Dipentamethylenethiuram tetrasulfide *8 2-Mercaptobenzothiazole

                                  TABLE 3__________________________________________________________________________                                      Adhesive  Adhesive                            strength  composition        Adherends       Curing conditions                                      (kgf/20 mm)__________________________________________________________________________Example1      A     Vulcanized EPDM composition                        Allowed to stand at                                      4.2        A-vulcanized EPDM                        room temperature for 6        composition A   days2      B     Vulcanized EPDM composition                        Heated at 80° C. for                                      4.8        A-vulcanized EPDM                        min and thereafter        composition A   allowed to stand at                        room temperature for 6 days3      C     Vulcanized EPDM composition                        Heated at 80° C. for                                      5.2        B-vulcanized EPDM                        min and thereafter        composition B   allowed to stand at                        room temperature for 6 days4      D     Vulcanized EPDM composition                        Allowed to stand at                                      3.5        B-vulcanized EPDM                        room temperature for        composition B   6 days5      A     Vulcanized EPDM composition                        Heated at 120° C. for                                      1.8        B-nylon plain cloth                        min and thereafter        of 100 denier   allowed to stand at                        room temperature for                        6 days6      A     Vulcanized EPDM composition                        Heated at 120°  C. for                                      1.9        B-polyester plain                        min and thereafter        cloth of 200 denier                        allowed to stand at                        room temperature for                        6 days7      A     Vulcanized IIR composition                        Allowed to stand at                                      2.7        C-vulcanized IIR                        room temperature        composition C   for 6 daysComparativeExample1      E     Vulcanized EPDM composition                        Heated at 80° C. for                                      0.9        B-vulcanized EPDM                        min and thereafter        composition B   allowed to stand at                        room temperature for                        6 days2      E     Vulcanized EPDM composition                        Heated at 120° C. for                                      0.5        B-nylon plain   min and thereafter        cloth of 100 denier                        allowed to stand at                        room temperature for                        6 days3      Slock *1        Vulcanized EPDM composition                        Heated at 80° C. for                                      1.2  8501  B-vulcanized EPDM                        min and thereafter        composition B   allowed to stand at                        room temperature for                        6 days4      Slock *1        Vulcanized EPDM composition                        Heated at 120° C. for                                      0.4  8501  B-polyester plain                        40 min and thereafter        cloth of 200 denier                        allowed to stand at                        room temperature                        for 6 days__________________________________________________________________________ Note: *1 A CRtype adhesive made by Sakai Chemical CO., LTD. for vulcanize EPDM compositions.

                                  TABLE 4__________________________________________________________________________  Adhesive                Adhesive strength  composition        Adherends         (kgf/20 mm)__________________________________________________________________________Example 8     A     Unvulcanized EPDM composition A-                          5.5        vulcanized EPDM composition A 9     B     Unvulcanized EPDM composition B-                          6.0        vulcanized EPDM composition B10     D     Unvulcanized EPDM composition B-                          5.7        vulcanized EPDM composition B11     A     Unvulcanized EPDM composition A-                          3.5        nylon plain cloth of 100 denier12     A     Unvulcanized EPDM composition A-                          3.2        polyester plain cloth of 200 denierComparativeExample 5     E     Unvulcanized EPDM composition A-                          1.5        vulcanized EPDM composition 6     E     Unvulcanized EPDM composition A-                          0.9        nylon plain cloth of 100 denier 7     Slock 8501        Unvulcanized EPDM composition A-                          0.5        polyester plain cloth of 200 denier__________________________________________________________________________

                                  TABLE 3__________________________________________________________________________                                      Adhesive  Adhesive                            strength  composition        Adherends       Curing conditions                                      (kgf/20 mm)__________________________________________________________________________Example13     A     Nylon plain cloth of 100                        Heated at 150° C. for                                      2.1        denier-nylon plain cloth                        min and thereafter        of 100 denier   allowed to stand at                        room temperature for                        6 days14     C     Polyester plain cloth of                        Heated at 120° C. for                                      1.6        200 denier-polyester                        40 min and thereafter        plain cloth of 200                        allowed to stand at        denier          room temperature for                        6 days15     A     Nylon plain cloth of                        Heated at 150° C. for                                      1.2        100 denier-polyester                        40 min and thereafter        plain cloth of 200                        allowed to stand at        denier          room temperature for                        6 daysComparativeExample 8     E     Nylon plain cloth of                        Heated at 150° C. for                                      0.4        100 denier-nylon plain                        40 min and thereafter        cloth of 100 denier                        allowed to stand at                        room temperature for                        6 days 9     Slock 8501        Nylon plain cloth of                        Heated at 150° C. for                                      0.5        100 denier-nylon plain                        40 min and thereafter        cloth of 100 denier                        allowed to stand at                        room temperature for                        6 days__________________________________________________________________________

                                  TABLE 6__________________________________________________________________________                              Type ofThe modified copolymer rubber      dialkylamine      Amount of             Non-    Type of acid                              and the amount       SolidsAdhesive   propylene             conjugated                     anhydride and the                              thereof (mole                                      Additive     concentrationcomposi-Intrinsic      (% by  diene and                     amount thereof                              per mole of                                      and amount                                            Organic                                                   (% bytion viscosity*1      weight)             iodine number                     (% by weight)                              acid anhydride)                                      (phr) solvent                                                   weight)__________________________________________________________________________F    1.4   22     None    Maleic anhydride                              Diethylamine                                      None  Toluene                                                   12                     1.5      0.85G    1.8   27     Ethylidenenor-                     Maleic anhydride                              Dibutylamine                                      FEF black                                            Xylene 10             bornene 5                     1.0      1.1     20H    1.0   45     None    Maleic anhydride                              Dibutylamine                                      None  Hexane  9                     4.2      1.0E    1.4   22     None    None     None    None  Toluene                                                   13__________________________________________________________________________ *1 The intrinsic viscosity was measured at 80° C. in toluene.

                                  TABLE 7__________________________________________________________________________                                      Adhesive  Adhesive                            strength  composition        Adherends       Curing conditions                                      (kgf/20 mm)__________________________________________________________________________Example16     F     Vulcanized EPDM composition A-                        Allowed to stand at                                      5.3        vulcanized EPDM composition A                        room temperature                        for 7 days17     G     Vulcanized EPDM composition A-                        Heated at 80° C.                                      5.7        vulcanized EPDM composition A                        for 40 min and                        thereafter allowed                        to stand at room                        temperature for 7 days18     H     Vulcanized EPDM composition B-                        Heated at 80° C.                                      4.8        vulcanized EPDM composition B                        for 40 min and                        thereafter allowed                        to stand at room                        temperature for 7 days19     H     Vulcanized EPDM composition B-                        Heated at 120° C.                                      2.1        nylon plain cloth                        for 40 min and        of 100 denier   thereafter allowed                        to stand at room                        temperature for 7 days20     H     Vulcanized EPDM composition B-                        Heated at 120° C.                                      2.4        polyester plain cloth                        for 40 min and        of 200 denier   thereafter allowed                        to stand at room                        temperature for 7 days21     F     Vulcanized IIR composition C-                        Allowed to stand at                                      2.9        vulcanized IIR  room temperature        composition C   for 7 daysComparativeExample10     E     Vulcanized EPDM composition B-                        Heated at 80° C.                                      1.1        vulcanized EPDM composition B                        for 40 min and                        thereafter allowed                        to stand at room                        temperature for 7 days11     E     Vulcanized EPDM composition B-                        Heated at 120° C.                                      0.6        nylon plain cloth                        for 40 min and        of 100 denier   thereafter allowed                        to stand at room                        temperature for 7 days12     Slock Vulcanized EPDM composition B-                        Heated at 80° C.                                      1.8  8501  vulcanized EPDM composition B                        for 40 min and                        thereafter allowed                        to stand at room                        temperature for 7 days13     Slock Vulcanized EPDM composition B-                        Heated at 120° C.                                      0.4  8501  polyester plain cloth                        for 40 min and        of 200 denier   thereafter allowed                        to stand at room                        temperature for 7 days__________________________________________________________________________

              TABLE 8______________________________________                         Adhesive  Adhesive               strength  composition          Adherends      (kgf/20 mm)______________________________________Example22       F         Unvulcanized EPDM                             6.1              composition A-              vulcanized EPDM              composition A23       G         Unvulcanized EPDM                             5.9              composition B-              vulcanized EPDM              composition B24       F         Unvulcanized EPDM                             3.8              composition A-              nylon plain cloth              of 100 denier25       F         Unvulcanized EPDM                             3.0              composition A-              polyester plain cloth              of 200 denierComparativeExample14       E         Unvulcanized EPDM                             1.8              composition A-              vulcanized EPDM              composition A15       E         Unvulcanized EPDM                             0.8              composition A-              nylon plain cloth              of 100 denier16       Slock     Unvulcanized EPDM                             0.5    8501      composition A-              polyester plain cloth              of 200 denier______________________________________

                                  TABLE 9__________________________________________________________________________                                      Adhesive  Adhesive                            strength  composition        Adherends       Curing conditions                                      (kgf/20 mm)__________________________________________________________________________Example26     A     Nylon plain cloth of 100                        Heated at 150° C. for                                      1.7        denier - nylon plain cloth                        40 min and thereafter        of 100 denier   allowed to stand at                        room temperature for                        7 days27     C     Polyester plain cloth of                        Heated at 120° C. for                                      2.8        200 denier - polyester                        40 min and thereafter        plain cloth of 200                        allowed to stand at        denier          room temperature for                        7 days28     A     Nylon plain cloth of 100                        Heated at 150° C. for                                      1.6        denier - polyester plain                        40 min and thereafter        cloth of 200 denier                        allowed to stand at                        room temperature for                        7 daysComparativeExample17     E     Nylon plain cloth of 100                        Heated at 150° C. for                                      0.3        denier - nylon plain cloth                        40 min and thereafter        of 100 denier   allowed to stand at                        room temperature for                        7 days18     Slock Nylon plain cloth of 100                        Heated at 150° C. for                                      0.5  8501  denier - nylon plain cloth                        40 min and thereafter        of 100 denier   allowed to stand at                        room temperature for                        7 days__________________________________________________________________________

                                  TABLE 10__________________________________________________________________________                            Type of  The modified copolymer rubber                            dialkylamine SolidsAd-    Intrin-      Amount of            Non-conjugated                    Acid anhydride                            and the amount                                         concen-                                              State after 30 daysEx-   hesive  sic propylene            diene and                    and the thereof (mole                                         tration                                              Change                                                    Ratio ofam-   compo-  vis-      (% by iodine  amount thereof                            per mole of                                    Organic                                         (% by                                              of    solutionple   sition  cosity      weight)            number  (% by weight)                            acid anhydride)                                    solvent                                         weight)                                              appearance                                                    viscosity__________________________________________________________________________                                                    *129 F   1.4 22    None    Maleic  Diethylamine                                    Toluene                                         12   No    1.1                    anhydride 1.5                            0.8530 H   1.0 45    None    Maleic  Dibutylamine                                    Hexane                                          9   No    1.1                    anhydride 4.2                            1.031 I   1.4 22    None    Maleic  None    Toluene                                         12   Precipitates                                                    5.5                    anhydride 1.5             Turbidity32 J   1.0 45    None    Maleic  None    Hexane                                          9   Precipitates                                                    8.7                    anhydride 4.2             Turbidity__________________________________________________________________________ *1 [Solution viscosity at 25° C. of an adhesive composition after being allowed to stand for 30 days]/[Initial solution viscosity at 25° C. of an adhesive composition]-

                                  TABLE 11__________________________________________________________________________The modified copolymer rubber                     Acid          Amount of            Non-     anhydride and/or                              Amount                                   of diethyl-      Amount of            conjugated                     dicarboxylic                              of   amine (mole                                         Additive  SolidsAdhesiveIntrinsic      propylene            diene    acid and the                              styrene                                   per mole                                         and       concentrationcomposi-viscosity*1      (% by and its  amount thereof                              (% by                                   of acid                                         amount                                              Organic                                                   (% bytion (100 ml/g)      weight)            iodine number                     (% by weight)                              weight)                                   anhydride)                                         (phr)                                              solvent                                                   weight)__________________________________________________________________________K    1.4   22    None     Maleic anhydride                              None None  None Toluene                                                   10                     1.3L    1.5   25    Ethylidene-                     Maleic anhydride                              None None  FEF  Xylene                                                   9            norbornene                     1.0                 black            Iodine Number                     Maleic acid         20            5        0.3M    1.6   27    None     Maleic anhydride                              3.6  None  None Toluene                                                   9.5                     4.7N    1.2   22    None     Maleic anhydride                              None 1.0   None Toluene                                                   11                     1.6O    1.4   22    None     None     None None  None Toluene                                                   10__________________________________________________________________________ Note: *1 The intrinsic viscosity was measured at 80° C. in toluene

                                  TABLE 12__________________________________________________________________________  Final adhesive composition        Diamine compound and        the amount thereof                         Adhesive  Adhesive        (mole per mole of the total amount of                                    Curing         strength  composition        acid anhydride and dicarboxylic acid)                          Adherends conditions     (kgf/20__________________________________________________________________________                                                   mm)Example33     K     Hexamethylenediamine                          Vulcanized EPDM                                    Allowed to     5.3        0.5               composition A-                                    stand at                          vulcanized EPDM                                    room temperature                          composition A                                    for 7 days34     L     Hexamethylenediamine                          Vulcanized EPDM                                    Heated at 80° C. for 40                                    min            6.1        carbamate 1       composition B-                                    and thereafter allowed to stand                          vulcanized EPDM                                    at room temperature for 7 days                          composition B35     M     Hexamethylenediamine                          Vulcanized EPDM                                    Allowed to stand                                                   4.6        carbamate 0.3     compositon B-                                    room temperature                          vulcanized EPDM                                    for 7 days                          composition B36     N     Hexamethylenediamine                          Vulcanized IIR                                    Heated at 80° C. for 40                                    min            4.1        carbamate 0.5     composition-                                    and thereafter allowed to stand                          vulcanized IIR                                    at room temperature for 7 days                          composition37     M     Hexamethylenediamine                          Vulcanized EPDM                                    Heated at 150° C. for 40                                    min            2.3        carbamate 0.5     composition B-                                    and thereafter allowed to stand                          nylon plain cloth                                    at room temperature for 7 days                          of 100 denier38     M     Hexamethylenediamine                          Vulcanized EPDM                                    Heated at 150° C. for 40                                    min            3.0        0.5               composition B-                                    and thereafter allowed to stand                          polyester plain cloth                                    at room temperature for 7 days                          of 200 denier39     K     None              Vulcanized EPDM                                    Allowed to stand at                                                   4.4m                          composition A-                                    temperature for 7 days                          vulcanized EPDM                          composition A40     M     None              Vulcanized EPDM                                    Heated at 150° C. for 40                                    min            2.0                          composition B-                                    and thereafter allowed to stand                          nylon plain cloth                                    at room temperature for 7 days                          of 100 denierComparativeExample19     O     Hexamethylenediamine                          Vulcanized EPDM                                    Allowed to stand at                                                   1.1m        carbamate 0.5     composition A-                                    temperature for 7 days                          vulcanized EPDM                          composition A__________________________________________________________________________

                                  TABLE 13__________________________________________________________________________  Final adhesive composition        Diamine compound and               Adhesive  Adhesive        the amount thereof                 strengthExample  composition        (mole per mole of acid anhydride)                         Adherends         (kgf/20__________________________________________________________________________                                           mm)41     K     Hexamethylenediamine                         Unvulcanized EPDM composition                                           7.5        0.5              Unvulcanized EPDM composition A42     N     Hexamethylenediamine                         Unvulcanized EPDM composition                                           6.8        carbamate 0.5    Unvulcanized EPDM composition B43     N     Hexamethylenediamine                         Unvulcanized EPDM composition                                           4.2        carbamate 0.5    polyester plain cloth of 200 denier44     K     None             Unvulcanized EPDM composition                                           5.3                         Unvulcanized EPDM composition__________________________________________________________________________                         A

                                  TABLE 14__________________________________________________________________________  Final adhesive composition        Diamine compound        and the amount thereof                     Adhesive  Adhesive        (mole per mole of the total amount of                                    Curing         strength  composition        acid anhydride and dicarboxylic acid)                          Adherends conditions     (kgf/20__________________________________________________________________________                                                   mm)Example45     K     Hexamethylenediamine                          Nylon plain cloth of                                    Heated at 120° C. for 40                                    min            1.7        carbamate 0.5     100 denier - nylon                                    and thereafter allowed to stand                          plain cloth of                                    at room temperature for                          100 denier                                    7 days46     N     Hexamethylenediamine                          Nylon plain cloth of                                    Heated at 120° C. for 40                                    min            1.9        carbamate 0.5     100 denier - nylon                                    and thereafter allowed to stand                          plain cloth of                                    at room temperature for                          100 denier                                    7 days47     N     Hexamethylenediamine                          Polyester plain cloth                                    Heated at 150° C. for 40                                    min            2.5        1                 of 200 denier-                                    and thereafter allowed to stand                          polyester plain cloth                                    at room temperature for                          of 200 denier                                    7 days48     K     None              Nylon plain cloth of                                    Heated at 120° C. for 40                                    min            1.3                          100 denier-                                    and thereafter allowed to stand                          nylon plain cloth                                    at room temperature for                          of 100 denier                                    7 daysComparativeExample20     O     Hexamethylenediamine                          Nylon plain cloth of                                    Heated at 120° C. for 40                                    min            0.5        carbamate 0.5     100 denier-                                    and thereafter allowed to stand                          nylon plain cloth                                    at room temperature for                          of 100 denier                                    7 days__________________________________________________________________________
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Classifications
U.S. Classification156/331.6, 525/285, 525/379, 525/301, 524/531, 525/382
International ClassificationC09J151/06, C08F8/32
Cooperative ClassificationC08F8/32, C09J151/06
European ClassificationC09J151/06, C08F8/32
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